Thermoplastic elastomer composition

ABSTRACT

A thermoplastic elastomer composition and method of making the thermoplastic elastomer are disclosed. The thermoplastic elastomer may comprise a polymer blend. The polymer bland may comprise a non-crosslinked elastomer, oil, polyethylene, and antioxidant. The oil may be from about 15 wt. % to about 50 wt. % oil. The polyethylene may be from about 3 wt. % to about 30 wt. %. The antioxidant may be from about 0 to about 0.5 wt. %.

RELATED PATENT APPLICATIONS

This application claims priority date of U.S. provisional applicationNo. 62/837,168, which was filed on Apr. 22, 2019. The entire disclosuresof which are incorporated by reference herein.

TECHNICAL FIELD

The present disclosure relates generally to thermoplastic elastomericcompositions and more specifically to thermoplastic elastomericcompositions with low compression set and good melt strength.

BACKGROUND

A problem that is becoming more evident these days within the wineindustry is that a great number of traditionally naturally sealed winesare damaged by cork that is tainted, ill-fitting or deteriorated.

It is estimated that around 5-10% of all wines have been be affected tosome degree and in some cases the wine will have to be discarded becausethe cork is “corked”, meaning that the porous and imperfect material(wood bark) was tainted or infected, and during its contact with thewine, it altered its chemistry with damaging results to the quality ofthe wine. The “corked wine” will be affected and depending of theseriousness of the taint, it could show symptoms that go from mustysmell, to a change in the tastes of the wine, which becomes flat andbodiless.

Therefore, there is a need to develop synthetic wine cork withelastomeric materials that have low compression set and good meltstrength.

SUMMARY

According to a first aspect, the thermoplastic elastomer may comprise apolymer blend. The polymer blend may comprise a non-crosslinkedelastomer, oil, polyethylene, and anti-oxidant. The oil may be fromabout 15 wt. % to about 50 wt. %. The polyethylene may be from about 3.0wt. % to about 30 wt. %. The anti-oxidant may be from about 0 to about0.5 wt. %.

In certain aspects, the oil comprises mineral oil.

In certain aspects, the non-crosslinked elastomer may comprise styrenicblock copolymer.

In certain aspects, the styrenic block copolymer may be selected from agroup consisting of styrene-ethylene-butadiene-styrene polymer,styrene-ethylene butylene-styrene, styrene-ethylene propylene-styrene(SEPS), hydrogenated polybutadiene, hydrogenated polyisoprene,hydrogenated styrene-isoprene random copolymer, styrene-ethylenepropylene (SEP) block copolymer, styrene-ethylene ethylenepropylene-styrene (SEEPS), and hydrogenated styrene-butadiene randomcopolymer.

In certain aspects, the styrenic block copolymer may comprisestyrene-ethylene-butylene-styrene polymer.

In certain aspects, the styrenic block copolymer may comprise about 20wt. % to about 50 wt. % styrene-ethylene-butylene-styrene polymer.

In certain aspects, the styrene-ethylene-butylene-styrene polymer totalmolecular weight is from 100,000 to 440,000 g/mol.

In certain aspects, the mineral oil may comprise paraffinic oil.

In certain aspects, the styrene-ethylene-butylene-styrene polymer totalmolecular weight is from 200,000 g/mol to 440,000 g/mol. In certainaspects, the polyethylene may comprise linear low density polyethylene(LLDPE).

In certain aspects, the styrene-ethylene-butylene-styrene polymer totalmolecular weight is from 240,000 g/mol to 440,000 g/mol. In certainaspects, linear low density polyethylene has melt flow index of about0.5 to about 10.0 g/10 min, measured at 230° C., employing 2.16 kilogram(kg) weight.

In certain aspects, the thermoplastic elastomer has Shore A hardnessfrom about 30 to 95A.

In certain aspects, the thermoplastic elastomer has a weight percentratio of non-crosslinked elastomer to oil, when present, from about 0.4to about 2.5.

In certain aspects, the weight percent ratio is from about 0.7 to about1.5.

In certain aspects, the thermoplastic elastomer has melt viscosity atshear rate of 67 1/s of about 200 to about 2000 Pa·s, measured at 200°C.

In certain aspects, the thermoplastic elastomer has melt viscosity atshear rate of 67 1/s of about 500 to about 1300 Pa·s, measured at 200°C.

In certain aspects, the thermoplastic elastomer has melt viscosity atshear rate of 67 1/s of about 200 to about 500 Pa·s, measured at 200° C.

In certain aspects, the thermoplastic elastomer has melt viscosity atshear rate of 67 1/s of about 700 to about 1100 Pa·s, measured at 200°C.

In certain aspects, the non-crosslinked elastomer total molecular weightis from about 100,000 to about 440,000 g/mol.

In certain aspects, the non-crosslinked elastomer total molecular weightis from about 200,000 to about 400,000 g/mol.

According to a second aspect, a thermoplastic elastomer may comprise apolymer blend. The polymer blend may comprise a styrenic blockcopolymer, oil, polyethylene, anti-oxidant. The oil may be from about 15wt. % to about 50 wt, %. The polyethylene may be from about 3 wt. % toabout 30 wt, %. The anti-oxidant may be from about 0 to about 0.5 wt. %anti-oxidant. The thermoplastic elastomer may have melt viscosity atshear rate of 67 1/s of about 200 to about 2000 measured at about 200°C. According to a second aspect, a thermoplastic elastomer may comprisea polymer blend. The polymer blend may comprise a styrenic blockcopolymer, oil, polyethylene, and anti-oxidant. The oil may be fromabout 15 wt. % to about 50 wt. %. The polyethylene may be from about 3wt. % to about 30 wt. %. The anti-oxidant may be from about 0 to about0.5 wt. % anti-oxidant. The thermoplastic elastomer may have a weightpercent ratio of styrenic block copolymer to oil, when present, fromabout 0.4 to about 2.5. The styrenic block copolymer may be selectedfrom a group consisting of styrene-ethylene-butylene-styrene polymer,styrene-ethylene butylene-styrene, styrene-ethylene propylene-styrene(SEPS), styrene-ethylene propylene (SEP) block copolymer,styrene-ethylene ethylene propylene-styrene (SEEPS), and hydrogenatedstyrene-butadiene random copolymer.

DETAILED DESCRIPTION

In the following description, well-known functions or constructions arenot described in detail because they may obscure the disclosure inunnecessary detail. For this disclosure, the following terms anddefinitions shall apply. 1271 Reference throughout this specification to“one embodiment” or “an embodiment” means that a particular feature,structure, or characteristic described in connection with the embodimentis included in at least one embodiment of claimed subject matter. Thus,the appearances of the phrase “in one embodiment” or “an embodiment” invarious places throughout this specification are not necessarily allreferring to the same embodiment. Furthermore, the particular features,structures, or characteristics may be combined in one or moreembodiments.

Additionally, variations to the disclosed embodiments can be understoodand effected by the skilled person in practicing the claimed disclosure,the disclosure, and the appended claims. In the claims, the word“comprising” does not exclude other elements or steps, and theindefinite article “a” or “an” does not exclude a plurality. The merefact that certain measures are recited in mutually different dependentclaims does not indicate that a combination of these measures cannot beused to advantage.

Also, two or more steps may be performed concurrently or with partialconcurrence. Further, the steps of the method may be performed in anorder different from what has been disclosed. Such variation will dependon the process hardware systems chosen and on designer choice. All suchvariations are within the scope of the disclosure. Additionally, eventhough the disclosure has been described with reference to specificexemplifying embodiments thereof, many different alterations,modifications and the like will become apparent for those skilled in theart.

Embodiments include thermoplastic elastomeric material compositions,processes for preparing the compositions and articles of manufactureprepared from the compositions. In one embodiment, the thermoplasticelastomeric composition is provided comprising a polymer blend of about15% to about 50% styrene-ethylene-butadiene-styrene (SEBS) polymer; fromabout 15% to about 50% oil; from about 3.0% to about 30% polyethylene;and from about 0 to about 0.5% anti-oxidant.

As used herein, the term “polymer” refers to the product of apolymerization reaction, and is inclusive of homopolymers, copolymers,terpolymers, etc.

As used herein, unless specified otherwise, the term “copolymer(s)”refers to polymers formed by the polymerization of at least twodifferent monomers. For example, the term “copolymer” includes thecopolymerization reaction product of ethylene and an alpha-olefin, suchas 1-hexene. However, the term “copolymer” is also inclusive of, forexample, the copolymerization of a mixture of ethylene, propylene,1-hexene, and 1-octene.

As used herein, when a polymer is referred to as “comprising a monomer,”the monomer is present in the polymer in the polymerized form of themonomer or in the derivative form the monomer.

As used herein, “molecular weight” means weight average molecular weight(“Mw”). Mw is determined using Gel Permeation Chromatography. MolecularWeight Distribution (“MWD”) may be defined or measured as Mw divided bynumber average molecular weight (“Mn”). (For more information, see U.S.Pat. No. 4,540,753 to Cozewith et al. and references cited therein, andin Ver Strate et al., 21 MACROMOLECULES, pp. 3360-3371 (1998)). The “Mz”value is the high average molecular weight value, calculated asdiscussed by A. R. Cooper in Concise Encyclopedia of Polymer Science andEngineering, pp. 638-639 (J. I. Kroschwitz, ed. John Wiley & Sons 1990).

The term “active agent” refers to a substance capable of deliveringspecial activity or function to users. Suitable active agents may be ina variety of geometric forms including discrete particles, fibers,flakes, rods, spheres, needles, particles coated with fibers and thelike.

The term “compression” refers to the process or result of pressing byapplying a force on an object, thereby increasing the density of theobject.

The terms “elastomeric,” “elastomer,” “elastic,” and other derivativesof “elastomeric” are used interchangeably and refer to materials havingelastomeric or rubbery properties. Elastomeric materials, such asthermoplastic elastomers and thermoplastic vulcanizates, are generallycapable of recovering their shape after deformation when the deformingforce is removed. Specifically, as used herein, elastomeric is meant tobe that property of any material which upon application of an elongatingforce, permits that material to be stretchable to a stretched lengthwhich is at least about 25 percent greater than its relaxed length, andthat will cause the material to recover at least 40 percent of itselongation upon release of the stretching elongating force. Ahypothetical example which would satisfy this definition of anelastomeric material in the X-Y planar dimensions would be a one (1)inch sample of a material which is elongatable to at least 1.25 inchesand which, upon being elongated to 1.25 inches and released, willrecover to a length of not more than 1.15 inches. Many elastomericmaterials may be stretched by much more than 25 percent of their relaxedlength, and can recover to substantially their original relaxed lengthupon release of the stretching, elongating force. In addition to amaterial being elastomeric in the described X-Y planar dimensions of astructure, including a web or sheet, the material can be elastomeric inthe Z planar dimension. Specifically, when a structure is compressivelyloaded, it displays elastomeric properties and will essentially recoverto its original position upon removal of the load. Compression set issometimes used to help describe such elastic recovery. When compressionis applied to an elastomeric structure, the structure may displayelastomeric properties and then recover to near its original positionupon relaxation.

The term “extensible” refers to a material that is generally capable ofbeing extended or otherwise deformed, but which does not recover asignificant portion of its shape after the extension or deforming forceis removed.

The term “flexible” refers to the ability of a material to bend under animposed load such that its Bending Modulus at 0.5 mm deflection is 1000g/mm or lower as measured by the Bending Modulus Test.

The term “thermoplastic” describes a material that softens and/or flowswhen exposed to heat and which substantially returns to its originalhardened condition when cooled to room temperature.

As used herein, “weight percent” or “wt. %”, unless noted otherwise,means a percent by weight of a particular component based on the totalweight of the composition containing the component. For example, if amixture contains three pounds of sand and one pound of sugar, then thesand comprises 75 wt. % (3 lbs. sand/4 lbs. total mixture) of themixture and the sugar 25 wt. %.

The term “crystalline” if employed, refers to a polymer or a segmentthat possesses a first order transition or crystalline melting point(Tm) as determined by differential scanning calorimetry (DSC) orequivalent technique. The term may be used interchangeably with the term“semicrystalline”. The term “amorphous” refers to a polymer lacking acrystalline melting point as determined by differential scanningcalorimetry (DSC) or equivalent technique.

As used herein, Melt Flow Rates (“MFR”) may be determined in accordancewith ASTM D1238 at 230° C. and 2.16 kg weight.

As used herein, Melt Indices (“MI”) or Melt Flow Index/Indices, also maybe known as Melt Flow Rates, which may be determined in accordance withASTM D1238 at 190° C. and 2.16 kg weight.

Unless otherwise indicated, all numbers expressing quantities ofingredients, properties such as molecular weight, reaction conditions,properties such as molecular weight, reaction conditions, and so forthused in the specification and claims are to be understood as beingmodified in all instances by the term “about.” Accordingly, unlessindicated to the contrary, the numerical parameters set forth in thefollowing specification and attached claims are approximations that mayvary depending upon the desired properties sought to be obtained by thepresent invention. At the very least, and not as an attempt to limit theapplication of the doctrine of equivalents to the scope of the claims,each numerical parameter should at least be construed in light ofreported significant digits and by applying ordinary roundingtechniques.

Notwithstanding that the numerical ranges and parameters set forth thebroad scope of the invention are approximations, the numerical valuesset forth in specific examples are reported as precisely as possible.Any numerical value, however, inherently contain certain errorsnecessarily resulting from the standard deviation found in theirrespective testing measures.

The thermoplastic elastomeric compositions may comprise a polymer blend.The polymer blend may comprise a non-crosslinked elastomer, oil,polyethylene, and an antioxidant.

Preferred styrenic block copolymers are those having the formulae: ABA,(A-B) nX, ABAB′ or ABA′B′ respectively, wherein A and A′ represent apoly (monovinyl aromatic) block and B and B′ represent hydrogenated poly(conjugated diene(s)) blocks, wherein n is an integer ≥2 and wherein Xis the remainder of a coupling agent. It will be appreciated that theblocks A and A′, and B and B′ respectively are equal or different fromeach other, in that the blocks A are larger than the blocks A′ and theblocks B are larger than B′ or B and B′ are equal.

Most preferred block copolymers have the formulae ABA or (A-B) nX,wherein A represents a polymer block of one or more monovinyl aromaticmonomers selected from styrene, C1-C4 alkyl styrene andC1-C4dialkylstyrene and in particular styrene, α-methyl styrene,o-methyl styrene or p-methyl styrene, 1,3-dimethylstyrene, p-tert-butylstyrene or mixtures thereof and most preferably styrene only, wherein Brepresents a polymer block of one or more conjugated diene monomerscontaining from 4 to 8 carbon atoms, such as 1,3-butadiene,2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene ormixtures thereof, and preferably butadiene or isoprene and mostpreferably butadiene.

Preferred block copolymers ABA or (A-B)_(n)X comprise substantially purepoly(styrene) blocks, each having a true molecular weight in the rangeof from 3 kg/mole to 50 kg/mole while the total apparent molecularweight is in the range of from 70 to 700 kg/mol and preferably from 100to 500 kg/mol. The molecular weights referred to in this specificationand claims can be measured with gel permeation chromatography (GPC)using polystyrene calibration standards, such as is done according toASTM 3536. GPC is a well-known method wherein polymers are separatedaccording to molecular size, the largest molecule eluting first. Thechromatograph is calibrated using commercially available polystyrenemolecular weight standards. The molecular weight of polymers measuredusing GPC so calibrated are apparent molecular weights, also known asstyrene equivalent molecular weights. The styrenic equivalent molecularweight may be converted to true molecular weight when the styreniccontent of the polymer and the vinyl content of the diene segments areknown. The detector used is preferably a combination ultraviolet andrefractive index detector. The molecular weights expressed herein aremeasured at the peak of the GPC trace, converted to true molecularweights, and are commonly referred to as “peak molecular weights”.

Preparation methods for such polymers may be found in U.S. Pat. Nos.3,231,635, 3,231,635, 3,231,635, 3,231,635, and 3,231,635, in U.S. Pat.No. 3,231,635. U.S. Pat. No. 3,231,635. U.S. Pat. No. 3,231,635, and inU.S. Pat. No. 3,231,635. Processes for the selective hydrogenation ofthe B blocks were known from e.g. U.S. Pat. No. 3,231,635. U.S. Pat. No.3,231,635. U.S. Pat. No. 3,231,635. U.S. Pat. Nos. 3,231,635, and3,231,635. The disclosures of these before mentioned documents areherein incorporated by reference.

Suitable representatives of said most preferred block copolymers arethose available under the trade names KRATON®, SEPTON™ and TUFTEC™, forinstance KRATON G 1650, KRATON G 1654. KRATON G 1651, KRATON G 1652,KRATON G 1633, KRATON G 1641, KRATON G 1657, KRATON A 1535, KRATON A1636, KRATON GRP 6924, SEPTON 4055, SEPTON 4077, TUFTEC H 1272, TSRCTaipol 6150, Taipol 6154, Taipol 6151, Taipol 6159, Sinopec 503T, 602Tand 604T comprising usually poly(conjugated diene) blocks beinghydrogenated until less than 10% of the original ethylenic unsaturation.

The block copolymers that may be used in this embodiment may be selectedfrom the group of styrene-ethylene butylene-styrene (SEBS),styrene-ethylene propylene-styrene (SEPS), hydrogenated polybutadiene,hydrogenated polyisoprene, hydrogenated styrene-isoprene randomcopolymer, styrene-ethylene propylene (SEP) block copolymer,styrene-ethylene ethylene propylene-styrene (SEEPS) and hydrogenatedstyrene-butadiene random copolymer.

The hydrogenation of random diene copolymers are described by authors E.W. Duck, J. R. Hawkins, and J. M. Locke, in Journal of the IRI, 6, 19,1972, which may be used as the highly saturated elastomer in thisinvention and is incorporated herein as a reference. The saturatedtriblock polymers, SEBS and SEPS, with styrenic end blocks are also usedin this invention as the saturated elastomers. SEBS and SEPS areobtained on the hydrogenation of triblock copolymers of styrenic andbutadiene or styrenic and isoprene and are known to be commerciallyavailable. Some commercially available examples of such elastomersinclude Kraton G series polymers. U.S. Pat. Nos. 3,686,364 and 3,865,776give some examples of block copolymers that may be used in the practiceof this invention and are incorporated herein by reference. It is highlypreferred that the highly saturated elastomer be SEBS having a boundstyrenic content that is within the range of 15 weight percent to about60 weight percent.

It is possible to use the saturated block copolymers that are modifiedversions of SEBS. Such modified block copolymers additionally have asubstantial number of styrenic units that are randomly distributed inthe rubber mid blocks of ethylene and butylene. These modified saturatedblock copolymers are supplied under Kraton ‘A’ series. Saturated blockcopolymers grades as mentioned in TPE 2003 RAPRA Conference Proceedings,Brussels, Belgium, Sep. 16-17, 2003, Paper 18, Page 157, and Paper 21,page 181 may also be used and are incorporated herein by reference.

In one embodiment, polystyrene-ethylene-butadiene-styrene (SEBS) blockcopolymer may include suitable SEBS copolymers that include those with ablock styrenic content of about 10 to about 35 wt. % based on the totalSEBS copolymer, and have Shore A hardness values of about 40 to about80.

The thermoplastic elastomeric may comprise about 0.1 wt. % to about 40wt. % polyethylene, more preferably about 1.0 wt. % to about 35 wt. %polyethylene, more preferably 3.0 wt. % to about 30 wt. % polyethylene,more preferably, 4.0 wt. % to about 25 wt. % polyethylene. Suitablepolyethylene may include high density polyethylene (HDPE), low densitypolyethylene (LDPE), and linear low density polyethylene (LLDPE). In oneembodiment, high molecular weight polyethylene compounds may be used. Inone embodiment, suitable linear low density polyethylene (LLDP)generally have melt indices of about 0.5 to about 10.0 g/10 min,measured at 230° C., employing 2.16 kilogram (kg) weight.

The thermoplastic elastomeric compositions may comprise up to about 60%wt. %, preferably about 15 wt. % to about 55 wt. % oil, more preferablyabout 15 wt. % to about 50 wt. % oil, for example. Suitable oil mayinclude mineral oil. Suitable mineral oil may include paraffinic oils(ASTM D2226 TYPE 104), or naphthenic oils (ASTM 103 & 104A). All aboveoils represent different cuts from the distillation of crude oil.

In addition, the thermoplastic elastomeric compositions may comprise upto about 2 wt. %, preferably up to about 1 wt. % anti-oxidant, morepreferably up to about 0.5% wt. % antioxidant. Suitable anti-oxidant mayinclude hindered phenols, thiol compounds, amines or phosphites.

The thermoplastic elastomeric compositions also may comprise up to about3 wt. % colorant. Suitable color pigments are known to those skilled inthe art and the exact amount of color pigment is readily empiricallydetermined based on the desired color characteristic of the compositionand the finished product.

The thermoplastic elastomeric compositions may also comprise up to about3 wt. %, preferably about 1 wt. %, of a processing aid such a metalstearate, soaps, an ultra-high molecular weight siloxane polymer orlubricants, in order to assist proper flow of the polymer melt throughthe injection molded barrel and dies and result in molded parts withgood surface characteristics. A suitable example is zinc stearate.

The thermoplastic elastomeric compositions may also optionally comprisestabilizers, such as heat stabilizer and/or light stabilizer, such asultraviolet light stabilizers, as well as combinations of heat and lightstabilizers. Heat stabilizers, like antioxidants, include phenolics,amines, phosphites, and the like, as well as combinations comprising atleast one of the foregoing heat stabilizers. Light stabilizers includelow molecular weight (having number-average molecular weights less thanabout 1,000 AMU) benzophenones or hindered amines, high molecular weight(having number-average molecular weights greater than about 1,000 AMU)hindered amines, benzotriazoles, hydroxyphenyl triazines, and the like,as well as combinations comprising at least one of the foregoing lightstabilizers. Optionally, various additives known in the art may be usedas needed to impart various properties to the composition, such as heatstability, stability upon exposure to ultraviolet wavelength radiation,long-term durability, and processability. The exact amount of stabilizeris readily empirically determined by the reaction employed and thedesired characteristics of the finished article, with up to about 3 wt.% possible, 1 wt. % preferred.

The thermoplastic elastomeric compositions and articles formed thereofmay be prepared in a process. In the present process, the polymer blendcomprised of a thermoplastic elastomer material, such asstyrene-ethylene-butadiene-styrene (SEBS) polymer in powder form, ispre-mixed with polyethylene, anti-oxidant, and oil using a high shearmixer or other such device to form a tumble mixed blend of thecomposition prior to being disposed into the hopper of the twin screwextruder, through which the premix is melted, mixed and pelletized in tothermoplastic elastomer pellets. The formed Thermoplastic elastomer canbe processed into different products such as wine corks, toothpicks andothers by extrusion process, injection molding and other polymerprocessing processes.

EXPERIMENTAL DETAILS

Mixing in a continuous process typically occurs in a twin-screw extruderthat was elevated to a temperature that was sufficient to melt thepolymer matrix with addition of all additives at the feed-throat, or byinjection or side-feeders downstream. Extruder speeds ranged from about50 to about 1200 revolutions per minute (rpm), and preferably from about300 to about 700 rpm, for example. Typically, the output from theextruder was pelletized for later processing. By the use of a twin-screwextruder, the blending components as shown hereunder were kneaded atfrom about 160° C. to about 220° C., and extruded into strands, whichwere then cut into pellets. For example, a lab twin screw extruderincluded 9 zones, with zone 1 about 160° C., zone 2 about 180° C., zone3 about 210° C., zone 4 about 210° C., zone 5 about 200° C., zone 6about 180° C., zone 7 about 160° C., zone 8 about 160° C., zone 9 about160° C. The pelletizer temperature may be 170° C.

Examples 1-4

A composition of pellet form was prepared in accordance with thecompounding recipe shown in Table 1, using a twin-screw extruder underconditions discussed in experiment details. The pellets wereinjection-molded to prepare a square sheet of 10 cm×10 cm. The sheet wascut by a dumbbell cutter to prepare test pieces for measurement. In thepreparation of the composition in the twin-screw extruder, Componentswere dry-blended; the blend was passed through the extruder. The resultsare shown in Table 2.

As is clear from Table 2, the Elastomer Compositions of this embodimentare elastomers having a low compression set, excellent elasticity andexcellent dynamic properties.

TABLE 1 14A 14B 14C 1A Raw Material Name pphr % pphr % pphr % phbr %SEBS 1633 100.00 31.50 100.00 31.50 100.00 30.35 100.00 32.00 Drakeol600 121.00 38.12 121.00 38.21 121.00 36.73 121.00 38.72 Polypropylene23.00 7.25 0.00 0.00 0.00 0.00 0.00 0.00 6523 Polypropylene 0.00 0.0023.00 7.25 0.00 0.00 0.00 0.00 Inspire 114 Polyastolyn 10.00 3.15 10.003.15 10.00 3.04 10.00 3.20 290 LLDPE 23.00 7.25 23.00 7.25 58.00 17.610.00 0.00 SP4030 Armoslip E 0.25 0.08 0.25 0.08 0.25 0.08 0.25 0.08Irogonox 0.20 0.06 0.20 0.06 0.20 0.06 0.21 0.07 1010 Vicron 25-11 40.0012.00 40.00 12.60 40.00 12.14 40.00 12.80 Polypropylene 0.00 0.00 0.000.00 0.00 0.00 41.00 13.12 CP360H TOTAL 317.45 100.00 317.45 100.00329.45 100.00 312.46 100.00 Density 0.990 1.008 0.997 0.982 (gram/cm²)

TABLE 2 Group 14A, 14B, 14C, 1A test result summary 14A 14B 14C 1AHardness, Shore A 61 62 64 60 Density, g/cm³ 0.98 0.99 0.99 0.98Compression Set, 34.41% 36.34% 29.15% 41.01% 70° C.@22 hrs TensileStrength, MPa 5.70 5.31 6.01 8.19 Tensile Elongation, % 436 288 142 571100% Modulus, MPa 2.89 3.63 4.87 2.66 300% Modulus, MPa 4.46 / / 4.24Viscosity(200° 1095.24 1168.71 1464.54 653.70 C.)@Shear Rats 67 1/S,Pa*s

Examples 5-9

A composition of pellet form was prepared in accordance with thecompounding recipe shown in Table 3, using a twin screw extruder underconditions discussed in experiment details. The pellets wereinjection-molded to prepare a square sheet of 10 cm×10 cm. The sheet wascut by a dumbbell cutter to prepare test pieces for measurement. In thepreparation of the composition in the twin screw extruder, Componentswere dry-blended; the blend was passed through the extruder. The resultsare shown in Table 4.

As is clear from Table 4, the Elastomer Compositions of this embodimentare elastomers having a low compression sets, excellent elasticity andgood melt strength.

TABLE 3 A B C D E Raw material Name pphr % pphr % pphr % phbr % phbr %SEBS 100.00 35.57 100.00 35.57 100.00 35.57 100.00 35.57 100.00 35.57503T Drakeol 121.00 43.04 121.00 43.04 121.00 43.04 121.00 4304 121.0043.04 34 LLDPE 30.00 10.67 15.00 5.34 0.00 0.00 45.00 16.01 60.00 21.34SP4030 PP6523 30.00 10.67 45.00 16.01 60.00 21.34 15.00 5.34 0.00 0.00BNX1010 0.14 0.05 0.14 0.05 0.14 0.15 0.14 0.05 0.14 0.05 TOTAL 281.14100.00 281.14 100.00 281.14 100.00 281.14 100.00 281.14 100.00

TABLE 4 A B C D E Hardness, Shore A 69 73    77 63    61    Density,g/cm³ 0.88 0.88 0.88 0.91 0.91 Compression Set, 45.1%  48% 54.7% 38.4% 34% 70° C.@22 hours Compression Set, 18.2% 18.8% 22.1%  15% 12.7% 23°C.@22 hours Tensile Tensile Strength, MPa 5.60 5.65 7.10 6.36 6.38Tensile Elongation, % 374 228    349 498    477    50% Modulus, MPa 3.103.95 4.59 2.09 1.50 100% Modulus, MPa 3.81 4.70 5.28 2.68 2.16 200%Modulus, MPa 4.60 5.42 5.99 3.56 3.30 300% Modulus, MPa 5.19 5.93 6.514.39 4.36 Rheology Viscosity(200° C.)@Shear 810.32 695.22  575.73916.81  1064.23   Rate 67 1/S, Pa*s

Examples 10-15

A composition of pellet form was prepared in accordance with thecompounding recipe shown in Table 5, using a twin screw extruder underconditions discussed in experiment details. The pellets wereinjection-molded to prepare a square sheet of 10 cm×10 cm. The sheet wascut by a dumbbell cutter to prepare test pieces for measurement. In thepreparation of the composition in the twin screw extruder, Componentswere dry-blended; the blend was passed through the extruder. The resultsare shown in Table 6.

As is clear from Table 6, the Elastomer Compositions of this embodimentare elastomers having a low hardness, compression sets, excellentelasticity, and good melt strength.

TABLE 5 177A 177B 177C 177D 178A 178B Raw Material Name pphr % pphr %pphr % phbr % phbr % ppbr % SEBS 0.00 0.00 0.00 0.00 0.00 0.00 100.0040.01 1633 SEBS 100.00 43.49 100.00 40.01 100.00 42.56 0.00 0.00 100.0039.69 100.00 37.32 1651 Drakeol 110.00 47.84 110.00 44.01 100.00 42.56110.00 44.01 110.00 43.66 116.00 43.29 600 Polypropylene 8.00 3.48 18.00720 16.00 6.81 18.00 7.20 Inspire 114 PP 6523 19.00 7.54 24.00 8.96Alathon ® 8.00 3.48 18.00 7.20 16.00 6.81 18.00 7.20 19.00 7.54 0.000.00 HDPE H5618 Irgonox 0.15 0.07 0.15 0.06 0.15 0.06 0.15 0.06 1010 BNX0.15 0.06 0.15 0.06 1010 Armoslip 0.50 0.22 0.50 0.20 0.50 0.21 0.500.20 0.50 0.20 0.20 0.19 E BNX 0.30 0.13 0.30 0.12 0.30 1.28 3.00 1.200.30 0.12 0.30 0.11 DLTDP MB50002 3.00 1.30 3.00 1.20 3.00 1.28 3.001.20 3.00 1.19 3.00 Silicone MASTER BATCH

TABLE 6 Hardness, Compression testing No. Shore A Set condition Protocol177A 41 41.8 70° C., 22 h ASTM D359B 177B 58 38 70° C., 22 h ASTM D359B177C 58 40.1 70° C., 22 h ASTM D359B 177D 59 35.7 70° C., 22 h ASTMD359B 178A 58 46.2 70° C., 22 h ASTM D359B 178B 60 45 70° C., 22 h ASTMD359B

The embodiments of the present compositions, processes and articles madethere from, although primarily described in relation to wine cork skinapplication, may be utilized in numerous other applications, bothnonautomotive and automotive vehicle applications such as interiorsheathing, including instrument panel skins, door panels, air bagcovers, roof liners, and seat covers.

It will be understood that a person skilled in the art may makemodifications to the embodiments shown herein within the scope andintent of the claims. While the present invention has been described ascarried out in specific embodiments thereof, it is not intended to belimited thereby but is intended to cover the invention broadly withinthe scope of the claims.

The above-cited patents and patent publications are hereby incorporatedby reference in their entirety. Although various embodiments have beendescribed with reference to a particular arrangement of parts, features,and like, these are not intended to exhaust all possible arrangements orfeatures, and indeed many other embodiments, modifications, andvariations may be ascertainable to those of skill in the art, Thus, itis to be understood that the invention may therefore be practicedotherwise than as specifically described above.

We claim:
 1. A thermoplastic elastomer composition, comprising, a polymer blend comprising a sole non-crosslinked elastomer, wherein the non-cross-linked elastomer comprises styrenic block copolymer is selected from a group consisting of styrene-butadiene-styrene polymer (SBS), styrene-ethylene butylene-styrene (SEBS), styrene-isoprene-styrene (SIS), styrene-isoprene-butadiene-styrene (SIBS), styrene-ethylene propylene-styrene (SEPS), styrene-ethylene propylene (SEP) block copolymer, styrene-ethylene ethylene propylene-styrene (SEEPS), hydrogenated polybutadiene, hydrogenated polyisoprene, hydrogenated styrene-isoprene random copolymer, poly (styrene-[(butadiene)_(1-x)-(ethylene-co-butylene)_(x)]-styrene), wherein x is the hydrogenated fraction of the molecule, and hydrogenated styrene-butylene random, wherein the non-crosslinked elastomer total molecular weight is from about 100,000 to about 440,000 g/mol; from about 25 wt. % to about 50 wt. % oil, wherein the oil comprises mineral oil, wherein the mineral oil comprises paraffinic oil; from about 3.0 wt. % to about 20 wt. % polyethylene, wherein the polyethylene comprises at least one of linear low density polyethylene (LLDPE) low density polyethylene (LDPE) or high density polyethylene (HDPE), wherein polyethylene has melt flow index of about 0.5 g/10 min to about 10.0 g/10 min, measured at 190° C., employing 2.15 kilogram (kg) weight; and from about 0 to about 0.5 wt. % anti-oxidant, wherein the thermoplastic elastomer composition has a weight percent ratio of non-crosslinked elastomer to oil from about 0.8:1 to about 1.1:1, wherein the thermoplastic elastomer composition exhibits compression set from about 30% to about 48%, measured at about 70° C. for about 22 hours per ASTM D359B, wherein the thermoplastic elastomer composition has a melt viscosity of 67 1/s of about 200 to about 2000 Pa·s, measured at 200° C.
 2. The thermoplastic elastomer composition of claim 1, wherein the styrenic block copolymer comprises styrene-ethylene-butylene-styrene polymer.
 3. The thermoplastic elastomer composition of claim 2, wherein the styrene-ethylene-butylene-styrene polymer is about 30 wt. % to about 50 wt. % in the polymer blend.
 4. The thermoplastic elastomer composition of claim 2, wherein the styrene-ethylene-butylene-styrene polymer total molecular weight is from about 100,000 to about 440,000 g/mol.
 5. The thermoplastic elastomer composition of claim 4, wherein the styrene-ethylene-butylene-styrene polymer total molecular weight is from about 200,000 g/mol to about 440,000 g/mol.
 6. The thermoplastic elastomer composition of claim 1, wherein the styrene-ethylene-butylene-styrene polymer total molecular weight is from about 240,000 g/mol to about 440,000 g/mol.
 7. The thermoplastic elastomer composition of claim 1, wherein the thermoplastic elastomer composition has Shore A hardness from about 20 to 95A.
 8. The thermoplastic elastomer composition of claim 1, wherein the thermoplastic elastomer composition has melt viscosity at shear rate of 67 1/s of about 500 to about 1300 Pa·s, measured at 200° C.
 9. The thermoplastic elastomer composition of claim 1, wherein the thermoplastic elastomer composition has melt viscosity at shear rate of 67 1/s of about 200 to about 500 Pa·s, measured at 200° C.
 10. The thermoplastic elastomer composition of claim 1, wherein the thermoplastic elastomer composition has melt viscosity at shear rate of 67 1/s of about 700 to about 1100 Pa·s, measured at 200° C.
 11. The thermoplastic elastomer composition of claim 1, wherein the non-crosslinked elastomer total molecular weight is from about 200,000 to about 400,000 g/mol.
 12. The thermoplastic elastomer composition of claim 1, wherein the non-crosslinked elastomer total molecular weight is from about 240,000 to about 400,000 g/mol.
 13. A thermoplastic elastomer composition, comprising, a polymer blend comprising a styrenic block copolymer, wherein the styrenic block copolymer is selected from a group consisting of styrene-butadiene-styrene polymer (SBS), styrene-ethylene butylene-styrene (SEBS), styrene-isoprene-styrene (SIS), styrene-isoprene-butadiene-styrene (SIBS), styrene-ethylene propylene-styrene (SEPS), styrene-ethylene propylene (SEP) block copolymer, styrene-ethylene ethylene propylene-styrene (SEEPS), hydrogenated polybutadiene, hydrogenated polyisoprene, hydrogenated styrene-isoprene random copolymer, poly (styrene-[(butadiene)_(1-x)-(ethylene-co-butylene)_(x)]-styrene), wherein x is the hydrogenated fraction of the molecule, and hydrogenated styrene-butylene random, wherein the styrenic block copolymer total molecular weight is from about 100,000 to about 440,000 g/mol; from about 30 wt. % to about 50 wt. % oil, wherein the oil comprises mineral oil, wherein the mineral oil comprises paraffinic oil; from about 3.0 wt. % to about 20 wt. % polyethylene, wherein the polyethylene comprises at least one of linear low density polyethylene (LLDPE) low density polyethylene (LDPE) or high density polyethylene (HDPE), wherein polyethylene has melt flow index of about 0.5 g/10 min to about 10.0 g/10 min, measured at 190° C., employing 2.15 kilogram (kg) weight; and from about 0 to about 0.5 wt. % anti-oxidant, wherein the thermoplastic elastomer composition has a weight percent ratio of styrenic block copolymer to oil from about 0.8:1 to about 1.1:1, wherein the thermoplastic elastomer composition does not comprise thermoplastic vulcanizate or olefin block copolymer, wherein the thermoplastic elastomer composition exhibits compression set from about 30% to about 48%, measured at about 70° C. for about 22 hours per ASTM D359B, wherein the thermoplastic elastomer composition has a melt viscosity of 67 1/s of about 200 to about 2000 Pa·s, measured at 200° C.
 14. The thermoplastic elastomer composition of claim 13, wherein the styrenic block copolymer comprises styrene-ethylene-butylene-styrene polymer.
 15. The thermoplastic elastomer composition of claim 13, wherein the styrene-ethylene-butylene-styrene polymer is about 25 wt. % to about 50 wt. % in the polymer blend.
 16. The thermoplastic elastomer composition of claim 13, wherein the styrene-ethylene-butylene-styrene polymer total molecular weight is from 200,000 to 440,000 g/mol.
 17. The thermoplastic elastomer composition of claim 13, wherein the styrene-ethylene-butylene-styrene polymer total molecular weight is from 240,000 g/mol to 440,000 g/mol.
 18. The thermoplastic elastomer composition of claim 13, wherein the styrene-ethylene-butylene-styrene polymer total molecular weight is from 100,000 g/mol to 440,000 g/mol.
 19. The thermoplastic elastomer composition of claim 13, wherein the thermoplastic elastomer composition has Shore A hardness from about 20 to about 95A.
 20. The thermoplastic elastomer composition of claim 13, wherein the thermoplastic elastomer composition has melt viscosity at shear rate of 67 1/s of about 500 to about 1300 Pa·s, measured at 200° C.
 21. The thermoplastic elastomer composition of claim 13, wherein the thermoplastic elastomer composition has melt viscosity at shear rate of 67 1/s of about 700 to about 1100 Pa·s, measured at 200° C.
 22. The thermoplastic elastomer composition of claim 13, wherein the thermoplastic elastomer composition has viscosity at shear rate of 67 1/s of about 800 to about 1000 Pa·s, measured at 200° C.
 23. The thermoplastic elastomer composition of claim 13, wherein the styrenic block copolymer total molecular weight is from 200,000 to 400,000 g/mol.
 24. The thermoplastic elastomer composition of claim 13, wherein the styrenic block copolymer total molecular weight is from 240,000 to 400,000 g/mol. 